Polymer adhesive seals for protected anode architectures

ABSTRACT

Protected anode architectures for active metal anodes have a polymer adhesive seal that provides an hermetic enclosure for the active metal of the protected anode inside an anode compartment. The compartment is substantially impervious to ambient moisture and battery components such as catholyte (electrolyte about the cathode), and prevents volatile components of the protected anode, such as anolyte (electrolyte about the anode), from escaping. The architecture is formed by joining the protected anode to an anode container. The polymer adhesive seals provide an hermetic seal at the joint between a surface of the protected anode and the container.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 60/713,668 filed Sep. 2, 2005, titled ADHESIVE SEALS FOR PROTECTEDACTIVE METAL ANODES. This provisional patent application is incorporatedherein by reference in its entirety for all purposes.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to electrode structures for usein batteries. More particularly, this invention relates to protectedanode architectures that provide a sealed enclosure for a protectedactive metal anode (e.g., Li) in order to facilitate itsincorporation/optimization into a variety of battery cell structures.

2. Description of Related Art

The low equivalent weight of alkali metals, such as lithium, render themparticularly attractive as a battery electrode component. However,alkali metal anodes based on Li (e.g., Li metal foil, LiSn, LiC₆) arehighly reactive in ambient atmosphere, and are known to corrode ordegrade in a variety of electrolytes, such as aqueous and evennon-aqueous systems. Accordingly, the incorporation of lithium basedanodes into electrochemical devices requires special processing, and theselection of suitable electrolytes is limited, as is the choice ofcathode system.

Typically, lithium battery manufacture is conducted in inertenvironments in order to guard against degradation of lithium until itis hermetically sealed within a battery cell container. Moreover, inconventional active metal batteries such as lithium batteries, thelithium electrode (anode), microporous separator (e.g, Celgard), andpositive electrode (cathode) are all in intimate contact with theorganic aprotic solvent in the liquid electrolyte. So, the choice ofbattery cell chemistry is limited to systems in which the electrolyte isstable to both the cathode and the anode. Moreover, conventional cellarchitectures do not permit optimization of electrolytes or cathode-sidesolvent systems without impacting anode stability or performance andvice-versa

Prior work in the present applicants' laboratories has led to thedevelopment of technology for protecting active metal anodes with highlyionically conductive protective membrane architectures. These protectedactive metal anode structures and associated electrochemical cells, aredescribed in applicants' co-pending published US Applications US2004/0197641, now U.S. Pat. No. 7,645,543, issued Jan. 12, 2010), US2005/0175894, now U.S. Pat. No. 7,282,295, issued Oct. 16, 2007), andtheir corresponding International Patent Applications WO 2005/038953 andWO 2005/083829, respectively. These developments represent majoradvances in active metal battery technology, for instance renderingpossible functional Li/air and Li/water batteries.

This technology would be further advanced by the development ofappropriate barrier seals that would facilitate and/or optimize theincorporation of these protected active metal anodes into a variety ofcell structures.

SUMMARY OF THE INVENTION

The present invention provides protected anode architectures comprisingprotected active metal anodes having polymer adhesive barrier seals, andmethods for their fabrication. The architecture provides an hermeticenclosure for the active metal anode inside an anode compartment. Thecompartment is substantially impervious to ambient moisture and batterycomponents such as catholyte (electrolyte about the cathode, and in someaspects catholyte may also comprise dissolved or suspended redox activespecies and redox active liquids), and prevents volatile components ofthe protected anode, such as anolyte (electrolyte about the anode), fromescaping. The architecture is formed by joining the protected anode toan anode container. The polymer adhesives of the instant inventionprovide an hermetic seal at the joint between a surface of the protectedanode and the container.

One aspect of the invention is to provide polymer adhesive seals forprotected anode architectures that facilitate their use inelectrochemical environments including aqueous solutions, water andwater-based electrolytes, air, dissolved redox species and othermaterials reactive to lithium and other active metals, including organicsolvents/electrolytes and ionic liquids; and for their incorporationinto battery cells including those of Li/seawater, Li/air, and advancedactive metal ion rocking chair batteries such as those consisting of aLiC₆ anode and comprising the class of transition metal intercalationcathodes including Li₃V₂(PO₄)₃, V₂O₅, V₆O₁₃, LiCoO₂, LiMn₂O₄, LiNiO₂,Li₃V₂P₃O₁₁F and the like.

The protected anodes comprise an active metal anode (e.g., Li, LiSn,LiC₆) protected on its surface by a protective membrane architecture.The membrane architecture has a first surface that is ionicallyconductive and chemically compatible with the active metal anode and asecond surface that is impervious, ionically conductive and chemicallycompatible with environments that are corrosive to the active metalanode (e.g., aqueous solutions). Accordingly, the active metal anode isin ionic continuity with the protective membrane architecture. By ioniccontinuity, it is meant that under an associated electric field and/orconcentration gradient active metal ions are transportable between theactive metal anode and the protective membrane architecture. Theprotective membrane architectures include ionically conductivecomposites, ionically conductive membranes and ionically conductiveprotective architectures and the like as described in applicants'co-pending applications incorporated by reference above.

Protected anodes comprising protective membrane architectures arechemically stable on one side to the active metal anode, and on theother side to ambient conditions and cathode environments (cathodestructures and catholyte). Protected anodes offer significant advantagesin that they enable the use of anode-incompatible materials, such ascatholyte, on the cathode side without deleterious impact on the anode,and vice versa.

Protected anodes and associated electrochemical structures in accordancewith the present invention are described in applicants' co-pendingpublished US Applications, US 2004/0126653 (Ser. No. 10/686,189; nowU.S. Pat. No. 7,282,296, issued), US 2004/0142244 (Ser. No. 10/731,771;now U.S. Pat. No. 7,282,302, issued), US 2004/0191617 (Ser. No.10/772,228; now U.S. Pat. No. 7,390,591, issued Jun. 24, 2008), US2004/0197641 (Ser. No. 10/772,157; now U.S. Pat. No. 7,645,543, issuedJan. 12, 2010) and US 2005/0175894 (Ser. No. 10/824,944; now U.S. Pat.No. 7,282,295, issued Oct. 16, 2007) incorporated by reference herein.

In accordance with the present invention, the protected anodes areintegrated into the framework of a protected anode architecture byjoining the protective membrane architecture of the protected anode toan anode container. The anode container in conjunction with theprotective membrane architecture provides the mechanical structure thatforms the anode compartment, which in turn fully encloses the activemetal anode. The polymer adhesive seals of the instant invention sealthe joint between the membrane architecture and the container.

Integrating the protected anodes into the framework of the protectedanode architecture facilitates their use in electrochemical cellstructures as the anode compartment completely decouples the activemetal anode from the cathode environment of the cell.

The architectures of the present invention are particularly useful forbatteries based on active metal, alloy or intercalation electrodes thatenable high energy density batteries such as alkali metal anodes such asLi or Na, alkali metal alloys (e.g., LiAl, LiSn, Na₄PB and LiAg), andintercalation compounds comprising active metal ions (e.g., LiC₆), allof which are highly reactive in ambient conditions and aqueousenvironments, and are also corroded in all but the most carefully chosenorganic aprotic electrolyte solutions. The de-coupling by the anodecompartment enables battery chemistries otherwise thought impracticalsuch as those based on active metal anodes in conjunction with aqueous(water) based cathodes, such as Li/air, Li/seawater and Li/metal-hydrideand the lithium alloy and lithium-ion variants of these. Moreover, italso allows for the independent optimization of anolyte and catholyte,which can have great benefit in the development of advanced rockingchair batteries such as high voltage Li-ion cells.

The seals of the present invention are comprised of polymeric adhesives.While no polymers are considered completely impermeable, the inventorshave discovered that certain polymeric adhesives are chemicallyresistant to anolyte and catholyte environments, and that theseadhesives also form a strong bond to the protective membranes and arethemselves impervious to the elements inside and/or outside the anodecompartment that they come in contact with. Moreover, the polymericadhesive seals of the instant invention can be applied at temperaturesand in environments that do not adversely affect the electrical andmechanical properties of the protective membrane, or other components ofthe anode architecture. The polymeric adhesive seals of the instantinvention are set at temperatures that avoid membrane stresses caused bythermal mismatch. Preferably the temperature for applying and settingthe seal does not exceed 350° C. More preferably the temperature is lessthan 200° C., and it is most preferred to apply and set the seal at oraround room temperature in an air environment. For example, in oneembodiment of the instant invention, a thermosetting epoxy basedpolymeric adhesive is used to seal and bond the container to themembrane architecture. This epoxy adhesive is settable at roomtemperature (about 25° C.) and provides a hermetic barrier and ischemically stable to both anolyte organic solvents (e.g., DME, diglyme,PC) and catholyte aqueous solutions (e.g., seawater, caustic, neutral,acidic).

The present invention is directed to protected anode architectureshaving polymeric adhesive seals and methods to configure the seals inorder to form a substantially impervious anode compartment, and theincorporation of the protected anode architectures into electrochemicalcell environments and structures such as battery cells.

These and other features of the invention will be further described andexemplified in the detailed description below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-C illustrate cross-sectional depictions of protected anodearchitectures in accordance with embodiments of the present invention.

FIGS. 2A-D illustrate various alternative configurations of a protectivemembrane architectures in accordance with the present invention.

FIG. 3 is a schematic illustration of a battery cell incorporating aprotected anode architecture in accordance with the present invention.

FIG. 4 depicts a plot of the discharge curve of the test cell of Example3 incorporating a protected anode architecture having polymer adhesiveseals, and in a seawater catholyte environment, in accordance with thepresent invention.

FIG. 5 depicts a plot of the discharge curve of the test cell of Example4 incorporating a protected anode architecture having polymer adhesiveseals and in an environment of an aqueous catholyte in accordance withthe present invention.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

Reference will now be made in detail to specific embodiments of theinvention. Examples of the specific embodiments are illustrated in theaccompanying drawings. While the invention will be described inconjunction with these specific embodiments, it will be understood thatit is not intended to limit the invention to such specific embodiments.On the contrary, it is intended to cover alternatives, modifications,and equivalents as may be included within the spirit and scope of theinvention as defined by the appended claims. In the followingdescription, numerous specific details are set forth in order to providea thorough understanding of the present invention. The present inventionmay be practiced without some or all of these specific details. In otherinstances, well known process operations have not been described indetail in order not to unnecessarily obscure the present invention.

Protected anode architectures 140 in accordance with the presentinvention are illustrated in FIGS. 1A-C. The architectures comprise aprotected anode 120, comprising an active metal anode 100 in ioniccontinuity with a protective membrane architecture 102, joined to ananode container 106 having an open end. By ionic continuity, it is meantthat under an associated electric field and/or concentration gradientactive metal ions are transportable between the active metal anode andthe protective membrane architecture. The joint between the protectedanode 120 and the container 106 is formed such that the protectivemembrane architecture 102 of the protected anode provides asubstantially impervious wall component over the open container end. Theanode container 106 in combination with the protective membrane 102provides a mechanical structure that forms a substantially imperviousanode compartment 130 that fully encloses the active metal anode 100. Inaccordance with the present invention, polymeric adhesives hermeticallyseal the joint between the membrane and the container, generally at 117.

For a material of the protected anode architecture to be substantiallyimpervious it is meant that the material provides a sufficient barrierto constituents that it contacts from the external and/or the internalenvironment of the anode compartment, such that anode performance is notdegraded. For example, for a material to be substantially impervious tothe external environment (e.g., moisture, aqueous and non-aqueouscatholytes, constituents from the cathode environment including redoxactive species and solvents and other active metal corrosive batterycomponent materials that would be damaging to the active metal anode) itprovides a sufficient barrier to the constituents of the externalenvironment that it contacts to prevent any such damage that woulddegrade anode performance from occurring. Likewise, for a material to besubstantially impervious to the internal environment of the anodecompartment, it provides a sufficient barrier to internal componentsthat it contacts, including volatile anolyte solvents, from escaping, toprevent degradation of the anode performance. The protected anodearchitectures are hermetically sealed in the sense that the anodecompartment is substantially impervious to both external and internalenvironments that it comes in contact with.

Adhesive polymer seals of the instant invention are substantiallyimpervious to at least one of the external and internal environments ofthe anode compartment. In one embodiment a polymer adhesive seal issubstantially impervious to both the external and internal environments;as such it can be used as the sole sealant to seal the container to theprotective membrane architecture, generally at 117. In anotherembodiment, more than one type of polymer adhesive seal is employed tofully seal-off the anode compartment: for example, one polymer adhesiveseals is substantially impervious to the external environment andanother polymer adhesive seal of a different structure or composition issubstantially impervious to the internal environment. In suchembodiments, the polymer adhesive seals are configured in such a mannerthat the anode compartment is substantially impervious to both theexternal and internal environments. The relative configuration of thepolymer adhesive seal(s) of the instant invention is described infurther detail by referring to detailed portions of the joint at 117between the anode container and protective membrane, for which theyseal.

Details of the joint at 117 are depicted in FIGS. 1A-C. The interface atthe joint between the anode container and the protective membrane is at111. There are also two edges at the interface of the joint where thecontainer and membrane meet: one interface edge is on the interior wallof the anode compartment, at 113, and the other is on the exterior wallof the anode compartment, at 115. The embodiments illustrated in FIGS.1A-C illustrate three possible embodiments of protected anodearchitectures in accordance with the present invention. In oneembodiment, illustrated in FIG. 1A, the joint between the protectedanode and the container is formed between the edge of the container walland the surface of the protective membrane, generally at 117. Thisembodiment provides a convenient platform for bonding and sealing duringfabrication. In another embodiment, illustrated in FIG. 1B, the edge ofthe protective membrane architecture is joined to the inner wall surfaceof the container, generally at 117. This embodiment minimizes theinactive area of the anode. In a third embodiment, illustrated in FIG.1C, the container wall includes an edge lip that provides a bonding andsealing platform. This embodiment enables thin walled containers, whilethe edge lip provides a convenient platform for bonding and sealing. Theembodiments illustrated in FIGS. 1. A-C exemplify the present inventionand are not intended to be limiting.

One or more polymer adhesive seals, in accordance with the invention,are set in the region of the joint at 117. In one embodiment the polymeradhesive seal is set at the interface, 111, and on both the interior andexterior wall edges, 113 and 115 respectively. In another embodiment aseal is set at the interface 111 only. In another embodiment a seal isset at the interface 111 and on one of the interface edges. Whereadhesive is applied to multiple points the same or a different type ofpolymer adhesive (e.g., one with a different composition or chemicalstructure) can be used at each point. In one specific embodiment, threedifferent types of polymer adhesive seals are employed at 111, 113, and115. In another specific embodiment one type of polymer adhesive seal isset at the interface edge on the interior wall of the anode compartmentand a different type of seal is set at the interface edge on theexterior wall of the anode compartment. Further details concerning therelative configuration of the polymer adhesive seals and the motivationfor setting the seals at various locations about the joint are describedlater in the specification.

The protected anode may optionally include a current collector 108,composed of a suitable conductive metal that does not alloy with orintercalate the active metal. When the active metal is lithium, examplesof suitable current collector materials include nickel or copper.Furthermore, an electronically conductive terminal, 110 in electroniccontinuity with the active metal anode directly provides for passage ofelectrons into and out of the anode compartment. For example theterminal may be in direct contact with the active metal anode or withthe current collector. The polymer adhesives of the present inventionalso provide a particularly suitable feed-through seal between theterminal connector and the container (e.g., the cover lid or containerwall), as they may be applied and set at temperatures that do notadversely affect other components of the anode architecture. Theterminal 110 may be a metal tab such as a foil or, as shown in FIG. 1, awire composed of nickel, stainless steel or copper. The tab is welded tothe current collector 108 or attached to the active metal anode 100 bytechniques that are known to those of skill in the art of batterymanufacture, including resistance welding, ultrasonic welding, andpressure. The architecture may also include structure for maintainingcontact among components inside the anode compartment.

The protected anode architectures of the present invention are usefulfor active metal electrodes (anodes) that are highly reactive in ambientconditions and can benefit from a protected anode structure. The activemetal anode 100 comprises at least one of an active metal, active metalalloying metal, active metal ion and active metal intercalating anodematerial.

The active metals are generally alkali metals (e.g., lithium, sodium orpotassium), alkaline earth metals (e.g., calcium or magnesium), and/orcertain transitional metals (e.g., zinc), and/or alloys of two or moreof these. The following active metals may be used: alkali metals (e.g.,Li, Na, K), alkaline earth metals (e.g., Ca, Mg, Ba), or binary orternary alkali metal alloys with Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In,Sb. Preferred alloys include lithium aluminum alloys, lithium siliconalloys, lithium tin alloys, lithium silver alloys, and sodium leadalloys (e.g., Na₄Pb). Preferred active metal electrodes (anodes) arecomposed of the alkali metals lithium (Li) or sodium (Na). Li isparticularly preferred.

Moreover, in a discharged state, the active metal anode may be an activemetal alloying metal such as aluminum, silicon or tin, or an activemetal intercalating material such as carbon or others well known in theart. The use of active metal intercalating materials that reversiblyintercalate and de-intercalate active metal ions such as Li ions and Naions provide beneficial characteristics. First of all, it allowsprolonged cycle life of the battery without the risk of formation ofactive metal dendrites. Preferred active metal intercalating materialshave a potential near that (e.g., within about 1 volt) of theircorresponding active metal (e.g., Li, Na). A preferred active metalintercalating material is carbon.

The protected anode architectures of the present invention enable activemetal anodes to be used in environments that if not for thesubstantially impervious anode compartment would not be possible.Moreover, the imperviousness of the enclosure enables anodes having avery long service life. Accordingly, in one embodiment of the instantinvention the active metal anodes have high area capacity such that theactive metal anode is at least 10 microns thick (e.g., a Li active metalanode having 10 micron thickness yields 2 mAh/cm²), and may be up to 1cm (e.g., a Li active metal anode having 1 cm thickness yields 2 Ah/cm²)or more thick. Some preferred thickness ranges are preferably between 10and 50 microns, 50 and 100 microns, 0.1 and 1 mm, 1 mm and 10 mm, 10 mmand 100 mm, and 100 mm and 500 mm thick.

Referring back to FIG. 1, the anode container 106 forms part of themechanical structure of the anode compartment. Accordingly, the materialof the container is substantially impervious and chemically compatiblewith elements that it directly contacts, from inside or outside theanode compartment. The container may comprise any suitable material,flexible or rigid, so long as it meets the prerequisite of substantialimperviousness and chemical stability; it may be composed of glass(e.g., Pyrex), metals such as stainless steel, aluminum, aluminumalloys, titanium, nickel coated aluminum and others; plastics such aspolypropylene, acrylics, PVC and others; plastic based composites suchas Garolite™, and epoxy/fiberglass composites and laminates, inparticular metal-plastic laminates such as Laminate 95014 (manufacturedby Lawson Mardon Flexible, Inc. in Shelbyville, Ky.).

The anode container, 106, may take on a number of configurations, forexample the container may be a single component or it may be composed ofseveral structural elements joined together. In a preferred embodiment,as illustrated in FIGS. 1A-C, the container comprises a wall structure105 having a first and second opening, and a cover lid 107. Thegeometric shape of the wall structure may be of any form, it istypically of square, circular or rectangular section, for examplecircular, and it has at least one open end for the placement of theprotective membrane architecture. In one method of fabricating theprotected anode architecture, once all components have been configuredinside the anode compartment and the membrane architecture of theprotected anode has been joined to the container wall such that itcovers the first opening, the final cover seal is made over the secondopening by joining the top cover to the wall structure. In oneembodiment the container cover comprises a silicone rubber stoppercompression sealed against the wall structure of the anode container.Preferably, the container cover comprises materials such as thosedescribed above for the material of the container and is bonded andsealed to the container wall structure using the polymer adhesive sealsand bonding agents of the instant invention.

The protective membrane architecture 102 is in ionic continuity with theactive metal anode 100 and selectively transports active metal ions intoand out of the anode compartment 130 while providing an imperviousbarrier to the environment external to the anode compartment. It alsoprovides a barrier to components inside the anode compartment fromescaping. Protective membrane architectures suitable for use in thepresent invention are described in applicants' co-pending published USApplications US 2004/0197641 and US 2005/0175894 and their correspondingInternational Patent Applications WO 2005/038953 and WO 2005/083829,respectively, incorporated by reference herein.

FIGS. 2A-D illustrate representative protective membrane architecturesfrom these disclosures suitable for use in the present invention. Theprotective membrane architectures provide a barrier to isolate an activemetal, active metal alloy or active metal ion anode in the anodecompartment from ambient and/or the cathode side of the cell whileallowing for efficient ion active metal ion transport into and out ofthe anode compartment. The architecture may take on several forms.Generally it comprises a solid electrolyte layer that is substantiallyimpervious, ionically conductive and chemically compatible with theexternal ambient (e.g., air or water) or the cathode environment.

Referring to FIG. 2A, the protective membrane architecture can be amonolithic solid electrolyte 202 that provides ionic transport and ischemically stable to both the active metal anode 201 and the externalenvironment. Examples of such materials are Na-β″ alumina, LiHfPO₄ andNASICON, Nasiglass, Li₅La₃Ta₂O₁₂ and Li₅La₃Nb₂O₁₂. Na₅MSi₄O₁₂ (M: rareearth such as Nd, Dy, Gd).

More commonly, the ion membrane architecture is a composite composed ofat least two components of different materials having different chemicalcompatibility requirements, one chemically compatible with the anodeenvironment in the interior of the anode compartment, the otherchemically compatible with the exterior; generally ambient air or water,and/or battery electrolytes/catholytes. By “chemical compatibility” (or“chemically compatible”) it is meant that the referenced material doesnot react to form a product that is deleterious to battery celloperation when contacted with one or more other referenced battery cellcomponents or manufacturing, handling, storage or external environmentalconditions. The properties of different ionic conductors are combined ina composite material that has the desired properties of high overallionic conductivity and chemical stability towards the anode, the cathodeand ambient conditions encountered in battery manufacturing. Thecomposite is capable of protecting an active metal anode fromdeleterious reaction with other battery components or ambient conditionswhile providing a high level of ionic conductivity to facilitatemanufacture and/or enhance performance of a battery cell in which thecomposite is incorporated.

Referring to FIG. 2B, the protective membrane architecture can be acomposite solid electrolyte 210 composed of discrete layers, whereby thefirst material layer 212 is stable to the active metal anode 201 and thesecond material layer 214 is stable to the external environment.Alternatively, referring to FIG. 2C, the protective membranearchitecture can be a composite solid electrolyte 220 composed of thesame materials, but with a graded transition between the materialsrather than discrete layers.

Generally, the solid state composite protective membrane architectures(described with reference to FIGS. 2B and C) have a first and secondmaterial layer. The first material layer (or first layer material) ofthe composite is ionically conductive, and chemically compatible with anactive metal electrode material. Chemical compatibility in this aspectof the invention refers both to a material that is chemically stable andtherefore substantially unreactive when contacted with an active metalelectrode material. It may also refer to a material that is chemicallystable with air, to facilitate storage and handling, and reactive whencontacted with an active metal electrode material to produce a productthat is chemically stable against the active metal electrode materialand has the desirable ionic conductivity (i.e., a first layer material).Such a reactive material is sometimes referred to as a “precursor”material. The second material layer of the composite is substantiallyimpervious, ionically conductive and chemically compatible with thefirst material. Additional layers are possible to achieve these aims, orotherwise enhance electrode stability or performance. All layers of thecomposite have high ionic conductivity, at least 10⁻⁷ S/cm, generally atleast 10⁻⁶ S/cm, for example at least 10⁻⁵ S/cm to 10⁻⁴ S/cm, and ashigh as 10⁻³ S/cm or higher so that the overall ionic conductivity ofthe multi-layer protective structure is at least 10⁻⁷ S/cm and as highas 10⁻³ S/cm or higher.

A fourth suitable protective membrane architecture is illustrated inFIG. 2D. This architecture is a composite 230 composed of an interlayer232 between the solid electrolyte 234 and the active metal anode 201whereby the interlayer is impregnated with anolyte. Thus, thearchitecture includes an active metal ion conducting separator layerwith a non-aqueous anolyte (i.e., electrolyte about the anode), theseparator layer being chemically compatible with the active metal and incontact with the anode; and a solid electrolyte layer that issubstantially impervious (pinhole- and crack-free) ionically conductivelayer chemically compatible with the separator layer and aqueousenvironments and in contact with the separator layer. The solidelectrolyte layer of this architecture (FIG. 2D) generally shares theproperties of the second material layer for the composite solid statearchitectures (FIGS. 2B and C). Accordingly, the solid electrolyte layerof all three of these architectures will be referred to below as asecond material layer or second layer.

A wide variety of materials may be used in fabricating protectivecomposites in accordance with the present invention, consistent with theprinciples described above. For example, in the solid state embodimentsof FIGS. B and C, the first layer (material component), in contact withthe active metal, may be composed, in whole or in part, of active metalnitrides, active metal phosphides, active metal halides active metalsulfides, active metal phosphorous sulfides, or active metal phosphorusoxynitride-based glass. Specific examples include Li₃N, Li₃P, LiI, LiBr,LiCl, LiF, Li₂S—P₂S₅, Li₂S—P₂S₅—LiI and LiPON. Active metal electrodematerials (e.g., lithium) may be applied to these materials, or they maybe formed in situ by contacting precursors such as metal nitrides, metalphosphides, metal halides, red phosphorus, iodine, nitrogen orphosphorus containing organics and polymers, and the like with lithium.A particularly suitable precursor material is copper nitride (e.g.,Cu₃N). The in situ formation of the first layer may result from anincomplete conversion of the precursors to their lithiated analog.Nevertheless, such incomplete conversions meet the requirements of afirst layer material for a protective composite in accordance with thepresent invention and are therefore within the scope of the invention.

For the anolyte interlayer composite protective architecture embodiment(FIG. 2D), the protective membrane architecture has an active metal ionconducting separator layer chemically compatible with the active metalof the anode and in contact with the anode, the separator layercomprising a non-aqueous anolyte, and a substantially impervious,ionically conductive layer (“second” layer) in contact with theseparator layer, and chemically compatible with the separator layer andwith the exterior of the anode compartment. The separator layer can becomposed of a semi-permeable membrane impregnated with an organicanolyte. For example, the semi-permeable membrane may be a micro-porouspolymer, such as are available from Celgard, Inc. The organic anolytemay be in the liquid or gel phase. For example, the anolyte may includea solvent selected from the group consisting of organic carbonates,ethers, lactones, sulfones, etc, and combinations thereof, such as EC,PC, DEC, DMC, EMC, 1,2-DME or higher glymes, THF, 2MeTHF, sulfolane, andcombinations thereof. 1,3-dioxolane may also be used as an anolytesolvent, particularly but not necessarily when used to enhance thesafety of a cell incorporating the structure. When the anolyte is in thegel phase, gelling agents such as polyvinylidine fluoride (PVdF)compounds, hexafluropropylene-vinylidene fluoride copolymers (PVdf-HFP),polyacrylonitrile compounds, cross-linked polyether compounds,polyalkylene oxide compounds, polyethylene oxide compounds, andcombinations and the like may be added to gel the solvents. Suitableanolytes will, of course, also include active metal salts, such as, inthe case of lithium, for example, LiPF₆, LiBF₄, LiAsF₆, LiSO₃CF₃ orLiN(SO₂C₂F₅)₂. In the case sodium, suitable anolytes will include activemetal salts such as NaClO₄, NaPF₆, NaAsF₆ NaBF₄, NaSO₃CF₃, NaN(CF₃SO₂)₂or NaN(SO₂C₂F₅)₂, One example of a suitable separator layer is 1 M LiPF₆dissolved in propylene carbonate and impregnated in a Celgardmicroporous polymer membrane.

The second layer (material component) of the protective composite may becomposed of a material that is substantially impervious, ionicallyconductive and chemically compatible with the first material orprecursor, including glassy or amorphous metal ion conductors, such as aphosphorus-based glass, oxide-based glass, phosphorus-oxynitride-basedglass, sulpher-based glass, oxide/sulfide based glass, selenide basedglass, gallium based glass, germanium-based glass, Nasiglass; ceramicactive metal ion conductors, such as lithium beta-alumina, sodiumbeta-alumina, Li superionic conductor (LISICON), Na superionic conductor(NASICON), and the like; or glass-ceramic active metal ion conductors.Specific examples include LiPON, Li₃PO₄.Li₂S.SiS₂, Li₂S.GeS₂.Ga₂S₃,Li₂O.11Al₂O₃, Na₂O.11Al₂O₃, (Na,Li)_(1+x)Ti_(2−x)Al_(x)(PO₄)₃(0.1≦x≦0.9) and crystallographically related structures,Li_(1+x)Hf_(2−x)Al_(x)(PO₄)₃ (0.1≦x≦0.9), Na₃Zr₂Si₂PO₁₂, Li₃Zr₂Si₂PO₁₂,Na₅ZrP₃O₁₂, Na₅TiP₃O₁₂, Na₃Fe₂P₃O₁₂, Na₄NbP₃O₁₂, Na-Silicates,Li_(0.3)La_(0.5)TiO₃, Na₅MSi₄O₁₂ (M: rare earth such as Nd, Gd, Dy)Li₅ZrP₃O₁₂, Li₅TiP₃O₁₂, Li₃Fe₂P₃O₁₂ and Li₄NbP₃O₁₂, and combinationsthereof, optionally sintered or melted. Suitable ceramic ion activemetal ion conductors are described, for example, in U.S. Pat. No.4,985,317 to Adachi et al., incorporated by reference herein in itsentirety and for all purposes.

A particularly suitable glass-ceramic material for the second layer ofthe protective composite is a lithium ion conductive glass-ceramichaving the following composition:

Composition mol % P₂O₅ 26-55%  SiO₂ 0-15% GeO₂ + TiO₂ 25-50%  in whichGeO₂ 0-50% TiO₂ 0-50% ZrO₂ 0-10% M₂O₃ 0-10% Al₂O₃ 0-15% Ga₂O₃ 0-15% Li₂O3-25%and containing a predominant crystalline phase composed ofLi_(1+x)(M,Al,Ga)_(x)(Ge_(1−y)Ti_(y))_(2−x)(PO₄)₃ where X≦0.8 and0≦Y≦1.0, and where M is an element selected from the group consisting ofNd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/orLi_(1+x+y)Q_(x)Ti_(2−y)Si_(y)P_(3−y)O₁₂ where 0≦x≦0.4 and 0≦y≦0.6, andwhere Q is Al or Ga. The glass-ceramics are obtained by melting rawmaterials to a melt, casting the melt to a glass and subjecting theglass to a heat treatment. Such materials are available from OHARACorporation, Japan and are further described in U.S. Pat. Nos.5,702,995, 6,030,909, 6,315,881 and 6,485,622, incorporated herein byreference.

The composite should have an inherently high ionic conductivity. Ingeneral, the ionic conductivity of the composite is at least 10⁻⁷ S/cm,generally at least about 10⁻⁶ to 10⁻⁵ S/cm, and may be as high as 10⁻⁴to 10⁻³ S/cm or higher. The thickness of the first precursor materiallayer should be enough to prevent contact between the second materiallayer and adjacent materials or layers, in particular, the active metalof the anode. For example, the first material layer for the solid statemembranes can have a thickness of about 0.1 to 5 microns; 0.2 to 1micron; or about 0.25 micron. Suitable thickness for the anolyteinterlayer of the fourth embodiment range from 5 microns to 50 microns,for example a typical thickness of Celgard is 25 microns.

The thickness of the second material layer is preferably about 0.1 to1000 microns, or, where the ionic conductivity of the second materiallayer is about 10⁻⁷ S/cm, about 0.25 to 1 micron, or, where the ionicconductivity of the second material layer is between about 10⁻⁴ about10⁻³ S/cm, about 10 to 1000 microns, preferably between 1 and 500microns, and more preferably between 10 and 100 microns, for exampleabout 20 microns.

Referring back to FIG. 1, the protective membrane architecture 102 isjoined to the anode container 106 such that it provides a substantiallyimpervious wall component over an open end of the container. The joint,at 117, is hermetically sealed by the polymeric adhesive seals of theinstant invention. The seals may be set on any surface of the protectivemembrane architecture, including the surface of the first materiallayer, precursor layer and/or solid electrolyte layer (second materiallayer). For example, in an embodiment whereby the protective membranearchitecture comprises a Cu₃N precursor layer the seal may be formed onthe surface of the Cu₃N precursor and/or on the surface of the solidelectrolyte layer (second material layer).

The protective membrane architectures, described above, comprise atleast one substantially impervious solid electrolyte layer (e.g., secondmaterial layer). In one embodiment of a protected anode architecture,the anode container is joined to the protective membrane architecture onthe surface of the solid electrolyte layer as it provides an imperviousplatform for bonding. In this embodiment the polymer adhesive seal isset at the joint, generally at 117 between the solid electrolyte layerof the protective membrane architecture 102 and the container 106,thereby forming a substantially impervious anode compartment having aninterior and exterior region. The polymer adhesive seals may be appliedat the interface, at 111, or at the edges of the joint, located in theinterior and on the exterior of the anode container, at 113 and 115respectively. For example, in an embodiment whereby the membranearchitecture comprises an anolyte interlayer, as illustrated in FIG. 2D,the polymeric adhesive seals are preferably formed on the surface of thesolid electrolyte layer (second material layer), 234.

The seals of the instant invention are comprised of polymeric adhesives.Polymeric adhesives have both physical and chemical properties that areadvantageous for forming a strong reliable barrier seal, includingchemical resistance, barrier properties, wetting behavior thatfacilitates flow and bonding for ease of fabrication, electricalinsulation, superior bond strength and ruggedness due, in part, to theirinherent ductility. Polymers have a robust chemistry that allow forcompositional and structural variations to tailor properties and afforda wide range of methods to apply and set the seals, such as by thermalcompression, hot-melting, dissolving or dispersing polymer(s) into acarrier solvent followed by brushing or spraying, as well as varioustechniques to cure the adhesive including visible/ultra-voilet exposure,heat, and chemical reaction.

An adhesive polymer seal in accordance with the present inventionprovides the required hermetic barrier while avoiding the drawbacksassociated with formation of a potential alternative sealing technique,such as a glass seal, for example.

Relative to a glass seal, the adhesive polymer seal avoids thermaldegradation of any of the materials being joined by the seal orotherwise in the an incorporating battery cell at the high temperatures(e.g., several hundred to 1000° C. or more) required to from a glassseal; is less brittle than a glass seal; and avoids the coefficient ofthermal expansion (CTE) mismatch stresses associated with such hightemperature processing of multiple materials. The adhesive polymer sealcan be formed below the melting or glass transition temperatures ofeither or any of the materials being joined by the seal, as it maygenerally be conducted in a room temperature or otherwise ambientenvironment.

The polymer adhesive seals of the instant invention may be elastomers,thermoplastics or thermosetting. The adhesives of this invention providea substantially impervious and chemically resistant seal at theinterface and edges, where the joint is made, between the protectivemembrane architecture and the anode container. The polymer adhesiveseals adhere to both the protective membrane architecture and anodecontainer surfaces, and the adhesive bond is able to withstand theoperating environment of the device for its intended service life. Whilenot a requirement, the polymer adhesive seals may also provide some orall of the bond strength necessary to join the membrane architecture tothe anode container. In a preferred embodiment the polymer adhesiveseals provide the necessary bond strength to join the anode container tothe membrane architecture, so additional bond agents at the joint areunnecessary.

While it is advantageous to use an adhesive polymer seal to provide thebond that joins the anode container to the protective membranearchitecture, bonding agents may be used to enhance the strength of thebonded joint. The bonding agents, in accordance with the presentinvention, do not need to provide barrier function or be chemicallyresistant to the elements inside or outside the anode compartment, asthey can be over-coated with polymer seals of the instant invention.

Particularly suitable bonding agents are, in fact, also polymericadhesives, and their advantages are similar to those described above forpolymer adhesive seals. The requirements of a bonding agent, however,are less restrictive than those of a seal, since it does not requirebarrier functionality or chemical resistance to anolyte or catholyte.Accordingly, a broad range of bonding agents are enabled by the seals ofthe instant invention. These include epoxy based bonding agents and heatsealable thermoplastics such as low density polyethylene (LDPE).

For example, in one embodiments the bonding agent is set at thecontainer/membrane interface, at 111, where there is a platform forbonding and an inner and outer edge to subsequently cover the bondingagent with substantially impervious chemically resistant polymeradhesive seals. For example, if the bonding agent is set at 111, thepolymer seals can be set on the interface edges, at 113 and 115, therebycovering the interface and isolating the bond agent.

The strength and stability of the bond formed by the polymer sealsand/or bonding agents of the instant invention may be facilitated bypre-treatment of the surface of the protective membrane architecture,generally on the surface of the substantially impervious solid stateelectrolyte. These include treatments to roughen the surface of themembrane such as chemical etching (acid or base) and mechanicalgrinding. A particularly suitable etchant is concentrated lithiumhydroxide. Moreover, the protective membrane architecture may compriseprimer coatings to enhance bonding. Accordingly, the surface of themembrane around its perimeter may be coated with a primer such as thinlayers of inorganic compounds chemically stable in catholytes andanolytes. The thickness range for such primer coatings are from about0.01 to 5 um, preferably from 0.05 to 0.5 um. Particularly suitableprimer coating compounds are metal nitrides such as SnN_(x) and titaniumnitride that may be prepared by physical vapor deposition such asreactive sputtering in a N₂ atmosphere. Other suitable primers includeoxides such In₂O₃, SnO₂, and TiO₂ that may be prepared by sol-gelmethod, thermal evaporation, chemical vapor deposition and by pyrolysis.

In one embodiment, the polymer is dissolved in a carrier solvent beforebeing applied onto the surface of the membrane and/or container toprovide a seal where the interface of the joint will be formed. Forexample, a particularly suitable barrier seal adhesive comprisespolyisobutylene (PIB) (Mw: 60,000 to 5,000,000) such as that supplied byExxon under the tradename of VISTONEX, which forms a strong and ruggedbond to the solid electrolyte layers of the protective membranearchitecture and has excellent chemical resistance to organic solventscommonly used for anolyte such as carbonates and good resistance toambient moisture and aqueous solutions. Dissolved in warm heptane asolution comprising PIB may be applied to the joint interface at 111 bybrush or spray coating the edge of the container wall and/or solidelectrolyte surface of the membrane architecture; the polymer seal bondsand sets as the solvent carrier evaporates. To further ensure anadequate seal, the PIB/heptane solution may be coated onto the interfaceedges at the joint, at 113 and 115.

In another embodiment, the polymer seal comprises a thermoplastic thatis applied by the application of heat such as melting (e.g., using ahot-melt applicator) or heating in combination with applied pressure(e.g., using thermal compression). Thermoplastics such as thosecomprising polyethylene (PE), polypropylene (PP), ethylene vinyl acetate(EVA), ethylene acrylic acid (EAA), fluorocarbons comprisingtetraflouroethylene, hexafluropropylene and the like, acid modifiedethylene acids such as those commonly referred to by the trademark ofSurlyn are also particularly useful. Moreover, hot melt/thermalcompression adhesives are advantageous in that they do not containcarrier solvents, eliminating the need for solvent removal. In onemethod of bonding and sealing the container to the membranearchitecture, a low-density polyethylene thermoplastic gasket is placedaround the edge of the container wall, at 111, and a bond is set to themembrane by the application of heat and pressure. Additionalthermoplastic seals (e.g., PE based) are then applied along the edges at113 and 115.

In another embodiment, the seal comprises a thermosetting polymeradhesive, cured by heat, chemical reaction, or radiation (e.g., exposureto ultraviolet). A particularly suitable thermosetting adhesive is epoxyformed by curing an epoxy resin comprising epoxide with a curing agent.Epoxy based adhesives are advantageous as a barrier seal in that theycombine a number of functional benefits including superior adhesiveproperties, dimensional stability, and excellent chemical resistance,particularly to aqueous environments. Preferably the epoxy adhesive iscured in a mild processing environment, such as less than 200° C. and inair. It is more preferred for the epoxy to be cured at room temperature.In a preferred embodiment the epoxy based adhesive is formed from aresin comprising epoxide and a curing agent comprising polyamide andcured at about 25 C. A specific epoxy adhesive formulation, Hysol E 120HP, sold by Loctite, has been found to be particularly effective. Thisepoxy forms a strong bond to solid electrolyte layers and can be set ina room temperature, air environment using a chemical curing agent(hardener) comprising a polyamide. Polymer seals comprising Hysol E 120HP have been found by helium leak-testing in our laboratory to behermetic, and in our tests where the seal is exposed to aqueoussolutions and non-aqueous solvents, the seal is found to be imperviousto solvents. In one method to fabricate the protected anode architecture(e.g., using Hysol E 120 HP), the epoxy resin is thoroughly mixed withthe hardener and applied to the edge of the wall of the anode container,generally at 117. The container is pressed against the protectivemembrane architecture on the surface of the solid electrolyte layerwhile the epoxy sets at 25 C for about 20 hours.

The polymer adhesive seals of the instant invention are sufficientlyimpervious to water preventing deleterious reaction of moisture with theactive metal anode over the useful life of the protected anode (e.g., 1week to 10 years or more, preferably about 1 month to 5 years). In oneembodiment of the protected anode, a non-aqueous liquid electrolyte isused in an interlayer between the active metal foil and the solidelectrolyte membrane. The seal should maintain the water content of thisnon-aqueous liquid electrolyte such that its moisture content, from thetime that it is sealed in the anode compartment, does not increasebeyond a level that would degrade anode structure or performance. Insome embodiments, a suitable seal will prevent an increase in moisturecontent by more than 50 ppm, preferably by more than 20 ppm, and morepreferably by more than 10 ppm. In the case of a fully solid-stateprotective membrane, the seal should maintain the moisture level of thecompartment to similarly low ppm_(H20) in the inert gas of the anodecompartment. Depending on the application, more than one type of polymeradhesive may be employed to seal the membrane architecture to thecontainer interface. The seals are generally set at the joint at 117.For example seals may be set at the joint interface at 111, and/or atthe interface edges on the interior and exterior wall of the anodecompartment, at 113 and 115 respectively. Due to the versatility of thechemistry and favorable fabrication conditions, polymer adhesives enablea great many variations for seal configurations, and that many morepossibilities exist in the case of employing multiple adhesive sealtypes. Accordingly, the seal configuration embodiments described in thisspecification are meant to exemplify the various possible sealconfigurations, they are not in any way meant to be limiting.

In one embodiment a polymer adhesive seal that is substantiallyimpervious to organic solvents of an anolyte impregnated in theinterlayer of a protective membrane architecture may be set at 113;while an outer polymer adhesive seal comprising a different polymercomposition or structure, with excellent barrier properties(substantially impervious) to moisture and aqueous solutions may be setat 115. In this instant embodiment, one of the polymer seals might alsobe capable of providing the necessary bond strength to join thecontainer to the membrane; accordingly, this seal could then also be setat the interface, at 111. Alternatively, a bonding agent, rather than apolymer adhesive seal, may be set at 111 to bond the joint. In such anembodiment polymer adhesive seals would be needed along the interfaceedges at 113 and 115. Moreover, multiple consecutive coating layers ofpolymer adhesive seals may be applied, including the re-application ofthe seal over an existing seal. This provides for an added degree ofreliability and is beneficial to close off leaks occurring at interfacegaps or direct leakage paths through cracks or pores of the bulk seal.In another embodiment a first polymer adhesive seal may be set along theinterface edge at 115 on the exterior wall surface of the anodecompartment and a second polymer adhesive seal having a differentcomposition or structure is coated over the first seal to provideprotection against the environment external to the anode.

In a preferred embodiment, a single type of polymer adhesive seal isadequate, to provide chemical resistance and a substantially imperviousbarrier to elements that it contacts from both inside and outside theanode compartment. Moreover, it is preferred that the polymer alsoprovides the necessary mechanical bond strength to join the membrane tothe container, so that no additional bonding agents are needed. In sucha configuration, the polymer seal is set at the joint, generally in theregion of 117; more specifically, it is preferred for the seal to be seton at least the interface, at 111 and may additionally be applied andset over the interface edges on the interior and exterior wall of theanode compartment, at 113 and 115, respectively. A particularly suitablepolymer adhesive seal that provides all the necessary requirements ofchemical resistance, barrier properties (substantial imperviousness toboth the internal and external environment of the anode compartment) andbond strength is an epoxy seal comprising polyamide, for example Hysol E120 HP sold by Loctite.

The protected anode architecture in accordance with the presentinvention facilitates the use of protected anodes in a variety ofenvironments including those that would otherwise be corrosive to theactive metal anode if not for the imperviousness of the anodecompartment. For example, at varying times the outer surface of thearchitecture may be exposed during manufacturing to ambient, or duringdevice operation the outer surface of the protected anode architecturemay be in contact with elements that are corrosive to the active metalof the anode, such as electrochemical environments including aqueoussolutions, water and water-based catholytes, air, and other materialsreactive to lithium and other active metals, including organicsolvents/catholytes and ionic liquids.

By effectively isolating (de-coupling) the anode from ambient and/orcathode, including catholyte (i.e., electrolyte about the cathode)environments, including such environments that are normally highlycorrosive to Li or other active metals, the protected anode architectureprotects from, and at the same time allows ion transport in and out ofthese potentially corrosive environments. In this way, a great degree offlexibility is permitted the other components of an electrochemicaldevice, such as a battery cell, made with the architecture. Isolation ofthe anode from other components of a battery cell or otherelectrochemical cell in this way allows the use of virtually anysolvent, electrolyte and/or cathode material in conjunction with theanode. Also, optimization of electrolytes or cathode-side solventsystems may be done without impacting anode stability or performance.

There are a variety of applications that could benefit from the use ofaqueous solutions, including water and water-based electrolytes, air,and other materials reactive to lithium and other active metals,including organic solvents/electrolytes and ionic liquids, on thecathode side of the cell with an active (e.g., alkali, e.g., lithium)metal or active metal intercalation (e.g., lithium alloy or lithium-ion)anode in a battery cell.

Battery Cells

The protected anode architectures of the present invention are usefullyadopted in battery cells. For example, the anode architecture 140 ofFIG. 1 can be paired with a cathode system 118 to form a cell 300, asdepicted in FIG. 3. The cathode system 118 comprises catholyte and acathode structure 116 comprising at least an electronically conductivecomponent, and it may also comprise an ionically conductive component,and an electrochemically active component. The catholyte is partially orfully retained inside the cathode structure; it may also be positionedin a designated volume between the cathode structure and the protectivemembrane (not shown), or impregnated inside an optional separator 114.The cathode system 118 may have any desired composition and, due to theisolation provided by the protective architecture 140, is not limited bythe anode or anolyte composition. In particular, the cathode system mayincorporate components which would otherwise be highly reactive with theanode active metal, such as aqueous materials, including water, aqueouscatholytes and air, metal hydride electrodes and metal oxide electrodes.

The cathode system 118, also referred to as the cathode environment,includes an electronically conductive component, an ionically conductivecomponent, and an electrochemically active component. The cathode systemmay also include an optional separator material 114, such as a Celgardmicroporous membrane or a cloth material such as a Zirconia cloth tokeep the cathode structure from contacting and possibly damaging thesolid electrolyte layer, and/or provide an ionically conductivereservoir for retaining catholyte. The cathode system 118 may have anydesired composition and, due to the isolation provided by the anodecompartment, is not limited by the anode or anolyte composition. Inparticular, the cathode system may incorporate components which wouldotherwise be highly reactive with the anode active metal, such asaqueous materials, including water, aqueous catholytes and air, metalhydride electrodes and metal oxide electrodes.

The catholyte may comprise a solid, liquid or gas. Moreover, thecatholyte may comprise electrochemically active constituents such as butnot limited to aqueous depolarizers, seawater, dissolved oxidants suchas oxygen dissolved in aqueous solutions and non-aqueous solvents,reversible redox couples such as vanadium redox species used in flowcell batteries, and particulate redox couples that may be suspended in aliquid solution. While in the illustrated schematic the cathodeenvironment 118 is not shown to be in contact with the polymer adhesiveseals, it should be appreciated by those of skill in the art that inmost common cell constructions and device applications, whereby thecathode environment comprises a liquid catholyte, the catholyte will bein contact with at least one of the seals, for example the seal at theexterior edge joint at 115 or the seal at the interface, at 111.Moreover, in some embodiments of an anolyte interlayer protectivemembrane architecture, the anolyte will also be in contact with at leastone of the seals, for example the seal at 113.

Battery cells of the present invention may include, without limitation,water, aqueous solutions, air electrodes and metal hydride electrodes,such as are described in applicants' co-pending published USApplications US 2004/0197641, now U.S. Pat. No. 7,645,543, issued Jan.12, 2010), and US 2005/0175894, now U.S. Pat. No. 7,282,295, issued Oct.16, 2007), incorporated herein by reference, and metal oxide electrodes,as used, for example, in conventional Li-ion cells.

The effective isolation between anode and cathode achieved by theprotective membrane architecture of the present invention also enables agreat degree of flexibility in the choice of catholyte systems, inparticular aqueous systems, but also non-aqueous systems. Since theprotected anode is completely decoupled from the catholyte, so thatcatholyte compatibility with the anode is no longer an issue, solventsand salts which are not kinetically stable to the active metal anode(e.g., Li metal) can be used.

For cells using water as an electrochemically active cathode material, aporous electronically conductive support structure can provide theelectronically conductive component of the cathode system. An aqueouselectrolyte (catholyte) provides ion carriers for transport(conductivity) of Li ions and anions that combine with Li. Theelectrochemically active component (water) and the ionically conductivecomponent (aqueous ctaholyte) will be intermixed as a single solution,although they are conceptually separate elements of the battery cell.Suitable catholytes for the Li/water battery cell of the inventioninclude any aqueous electrolyte with suitable ionic conductivity.Suitable electrolytes may be acidic, for example, strong acids like HCl,H₂SO₄, H₃PO₄ or weak acids like acetic acid/Li acetate; basic, forexample, LiOH; neutral, for example, sea water, LiCl, LiBr, LiI; oramphoteric, for example, NH₄Cl, NH₄Br, etc

The suitability of sea water as a catholyte enables a battery cell formarine applications with very high energy density. Prior to use, thecell structure is composed of the protected anode and a porouselectronically conductive support structure (electronically conductivecomponent of the cathode structure). When needed, the cell is completedby immersing it in sea water which provides the electrochemically activeand ionically conductive components. Since the latter components areprovided by the sea water in the environment, they need not transportedas part of the battery cell prior to it use (and thus need not beincluded in the cell's energy density calculation). Such a cell isreferred to as an “open” cell since the reaction products on the cathodeside are not contained. Such a cell is, therefore, a primary cell.

Secondary Li/water cells are also possible in accordance with theinvention. As noted above, such cells are referred to as “closed” cellssince the reaction products on the cathode side are contained on thecathode side of the cell to be available to recharge the anode by movingthe Li ions back across the protective membrane when the appropriaterecharging potential is applied to the cell.

As noted above and described further below, in another embodiment of theinvention, ionomers coated on the porous catalytic electronicallyconductive support reduce or eliminate the need for ionic conductivityin the electrochemically active material.

The electrochemical reaction that occurs in a Li/water cell is a redoxreaction in which the electrochemically active cathode material getsreduced. In a Li/water cell, the catalytic electronically conductivesupport of the cathode structure facilitates the redox reaction. Asnoted above, while not so limited, in a Li/water cell, the cell reactionis believed to be:Li+H₂O═LiOH+½H₂.The half-cell reactions at the anode and cathode are believed to be:Anode: Li=Li⁺ +e ⁻Cathode: e ⁻+H₂O═OH⁻+½H₂

Accordingly, the catalyst for the Li/water cathode promotes electrontransfer to water, generating hydrogen and hydroxide ion. A common,inexpensive catalyst for this reaction is nickel metal; precious metalslike Pt, Pd, Ru, Au, etc. will also work but are more expensive.

Also considered to be within the scope of Li (or other activemetal)/water batteries of this invention are batteries with a protectedLi anode and an aqueous catholyte composed of gaseous and/or solidoxidants soluble in water that can be used as active cathode materials(electrochemically active component). Use of water soluble compounds,which are stronger oxidizers than water, can significantly increasebattery energy in some applications compared to the lithium/waterbattery, where during the cell discharge reaction, electrochemicalhydrogen evolution takes place at the cathode surface. Examples of suchgaseous oxidants are O₂, SO₂ and NO₂. Also, metal nitrites, inparticular NaNO₂ and KNO₂ and metal sulfites such as Na₂SO₃ and K₂SO₃are stronger oxidants than water and can be easily dissolved in largeconcentrations. Another class of inorganic oxidants soluble in water areperoxides of lithium, sodium and potassium, as well as hydrogen peroxideH₂O₂.

The use of hydrogen peroxide as an oxidant can be especially beneficial.There are at least two ways of utilizing hydrogen peroxide in a batterycell in accordance with the present invention. First of all, chemicaldecomposition of hydrogen peroxide on the cathode surface leads toproduction of oxygen gas, which can be used as active cathode material.The second, perhaps more effective way, is based on the directelectroreduction of hydrogen peroxide on the cathode surface. Inprincipal, hydrogen peroxide can be reduced from either basic or acidicsolutions. The highest energy density can be achieved for a batteryutilizing hydrogen peroxide reduction from acidic solutions. In thiscase a cell with Li anode yields E⁰=4.82 V (for standard conditions).However, because of very high reactivity of both acids and hydrogenperoxide to unprotected Li, such cell can be practically realized onlyfor protected Li anode such as in accordance with the present invention.

For cells using air as an electrochemically active cathode material, theair electrochemically active component of these cells includes moistureto provide water for the electrochemical reaction. The cells have anelectronically conductive support structure electrically connected withthe anode to allow electron transfer to reduce the air cathode activematerial. The electronically conductive support structure is generallyporous to allow fluid (air) flow and either catalytic or treated with acatalyst to catalyze the reduction of the cathode active material. Anaqueous catholyte with suitable ionic conductivity or ionomer is also incontact with the electronically conductive support structure to allowion transport within the electronically conductive support structure tocomplete the redox reaction.

The air cathode system includes an electronically conductive component(for example, a porous electronic conductor), an ionically conductivecomponent with at least an aqueous constituent, and air as anelectrochemically active component. It may be any suitable airelectrode, including those conventionally used in metal (e.g., Zn)/airbatteries or low temperature (e.g., PEM) fuel cells. Air cathodes usedin metal/air batteries, in particular in Zn/air batteries, are describedin many sources including “Handbook of Batteries” (Linden and T. B.Reddy, McGraw-Hill, NY, Third Edition) and are usually composed ofseveral layers including an air diffusion membrane, a hydrophobic Teflonlayer, a catalyst layer, and a metal electronically conductivecomponent/current collector, such as a Ni screen. The catalyst layeralso includes an ionically conductive component/electrolyte that may beaqueous and/or ionomeric. A typical aqueous catholyte is composed of KOHdissolved in water. An typical ionomeric electrolyte is composed of ahydrated (water) Li ion conductive polymer such as a per-fluoro-sulfonicacid polymer film (e.g., du Pont NAFION). The air diffusion membraneadjusts the air (oxygen) flow. The hydrophobic layer preventspenetration of the cell's catholyte into the air-diffusion membrane.This layer usually contains carbon and Teflon particles. The catalystlayer usually contains a high surface area carbon and a catalyst foracceleration of reduction of oxygen gas. Metal oxides, for example MnO₂,are used as the catalysts for oxygen reduction in most of the commercialcathodes. Alternative catalysts include metal macrocycles such as cobaltphthalocyanine, and highly dispersed precious metals such at platinumand platinum/ruthenium alloys. Since the air electrode structure ischemically isolated from the active metal electrode, the chemicalcomposition of the air electrode is not constrained by potentialreactivity with the anode active material. This can allow for the designof higher performance air electrodes using materials that would normallyattack unprotected metal electrodes.

Another type of active metal/aqueous battery cell incorporating aprotected anode and a cathode system with an aqueous component inaccordance with the present invention is a lithium (or other activemetal)/metal hydride battery. For example, lithium anodes protected witha non-aqueous interlayer architecture as described herein can bedischarged and charged in aqueous solutions suitable as electrolytes ina lithium/metal hydride battery. Suitable catholytes provide a source orprotons. Examples include aqueous solutions of halide acids or acidicsalts, including chloride or bromide acids or salts, for example HCl,HBr, NH₄Cl or NH₄Br.

In addition to the aqueous, air, etc., systems noted above, improvedperformance can be obtained with cathode systems incorporatingconventional Li-ion battery cathodes and electrolytes, such as metaloxide cathodes (e.g., V₂O₅, V₆O₁₃, Li_(x)CoO₂, Li_(x)NiO₂, Li_(x)Mn₂O₄,LiFePO₄, Li₃V₂(PO₄)₃, and Li₃V₂P₃O₁₁F) and the binary, ternary ormulti-component mixtures of alkyl carbonates or their mixtures withethers as solvents for a Li metal salt (e.g., LiPF₆, LiAsF₆ or LiBF₄);or Li metal battery cathodes (e.g., elemental sulfur or polysulfides)and electrolytes composed of organic carbonates, ethers, glymes,lactones, sulfones, sulfolane, and combinations thereof, such as EC, PC,DEC, DMC, EMC, 1,2-DME, THF, 2MeTHF, and combinations thereof, asdescribed, for example, in U.S. Pat. No. 6,376,123, incorporated hereinby reference.

Moreover, the catholyte solution can be composed of only low viscositysolvents, such as ethers like 1,2-dimethoxy ethane (DME),tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,3-dioxolane (DIOX),4-methyldioxolane (4-MeDIOX) or organic carbonates likedimethylcarbonate (DMC), ethylmethylcarbonate (EMC), diethylcarbonate(DEC), or their mixtures. Also, super low viscosity ester solvents orco-solvents such as methyl formate and methyl acetate, which are veryreactive to unprotected Li, can be used. As is known to those skilled inthe art, ionic conductivity and diffusion rates are inverselyproportional to viscosity such that all other things being equal,battery performance improves as the viscosity of the solvent decreases.The use of such catholyte solvent systems significantly improves batteryperformance, in particular discharge and charge characteristics at lowtemperatures.

Ionic liquids may also be used in catholytes of the present invention.Ionic liquids are organic salts with melting points under 100 degrees,often even lower than room temperature. The most common ionic liquidsare imidazolium and pyridinium derivatives, but also phosphonium ortetralkylammonium compounds are also known. Ionic liquids have thedesirable attributes of high ionic conductivity, high thermal stability,no measurable vapor pressure, and non-flammability. Representative ionicliquids are 1-Ethyl-3-methylimidazolium tosylate (EMIM-Ts),1-Butyl-3-methylimidazolium octyl sulfate (BMIM-OctSO4),1-Ethyl-3-methylimidazolium hexafluorophosphate, and1-Hexyl-3-methylimidazolium tetrafluoroborate. Although there has beensubstantial interest in ionic liquids for electrochemical applicationssuch as capacitors and batteries, they are unstable to metallic lithiumand lithiated carbon. However, protected lithium anodes as described inthis invention are isolated from direct chemical reaction, andconsequently lithium metal batteries using ionic liquids are possible asan embodiment of the present invention. Such batteries should beparticularly stable at elevated temperatures.

EXAMPLES

The following examples provide details illustrating advantageousproperties and performance of protected anode architectures havingpolymer adhesive seals in accordance with the present invention. Theseexamples are provided to exemplify and more clearly illustrate aspectsof the present invention and are in no way intended to be limiting.

Example 1 Demonstration of Effectiveness of Polymer Adhesive Seal

A few ml of Hysol E 120 HP were dispensed from the 50 ml dual cartridge(Item 29353) onto a glass plate and thoroughly mixed. The mixed adhesivewas transferred to the end of a 9 cm long pyrex tube having an OD of 25mm and wall thickness of 1.5 mm and the adhesive coated pyrex tube waspressed against the top surface of a 1″×1″ glass-ceramic plate suppliedby the OHARA Corporation. The adhesive was cured at 25° C. for a periodof 18-20 hours. The bonded plate/tube assembly was attached to a Varian938-41 helium leak detector. The helium leak detector showed no leakthrough the seal when the volume was evacuated and the helium tracerprobe was used. The sensitivity of the detector was 2×10⁻¹⁰ atm cc/secfor helium.

Example 2 Testing of Protected Lithium Anodes Having Polymer AdhesiveSeals in Various Aqueous Catholytes

A number of protected anodes were constructed using seals between 1″×1″OHARA plates and glass tubes as described in Example 1. Lithiumelectrodes were fabricated by cutting circular disks of ⅝″ diameter fromlithium foil having a thickness of 0.2 to 4 mm. The lithium disks werepressed into a nickel foil current collector with a nickel wire forcurrent collection. An interlayer between the lithium electrode and theglass-ceramic solid electrolyte consisted of a microporous membraneimmersed in a non-aqueous solvent with a dissolved supportingelectrolyte salt. Microporous membranes were made from Celgard disks of13/16″ diameter cut from Celgard 3401 of 25 μm thickness. The Celgarddisks were placed inside the pyrex tube against the glass-ceramicmembrane, and 750 μl of _(—)1.0 M supporting electrolyte salt in organicsolvent. The electrolyte salts were chosen from the list: LiClO₄, LiPF₆,LiBF₄, LiAsF₆, LiSO₃CF₃, LiN(CF₃SO₂)₂, and LiN(SO₂C₂F₅)₂. Non-aqueoussolvents were chosen from organic carbonates: EC, PC, DMC, EMC andothers; ethers: 1,2-DME and higher glymes, THF, 2MeTHF, Dioxolane andothers, as well as their binary and ternary mixtures were used as thesolvents. The top of the protected anode compartment was then sealed bymeans of a silicone rubber stopper. The protected anode was thenimmersed in aqueous catholytes selected from the list: solutions inwater of LiCl, LiBr, LiI, NH₄Cl, NH₄Br, HCl, H₂SO₄, acetic acid, HClwith addition of H₂O₂, H₂SO₄ with addition of H₂O₂, LiOH, synthetic seawater and others. A variety of metal screens were used for waterelectrolysis and current collection including nickel and titanium screenand Exmet. At least 30 cells of this type were tested by constantcurrent discharge at temperatures ranging from −5° C. to 40° C., andcurrents ranging from 0.1 mA/cm² to 15 mA/cm². At least 6 cells weredischarged to 100% of the available capacity of lithium, indicating ahermetic seal since any permeation of moisture into the anodecompartment would significantly reduce the lithium capacity. The sealshowed long-term stability in all aprotic non-aqueous electrolytestested as well as in neutral, acidic and basic aqueous electrolytes asevidence by no visible evidence of seal degradation, no visual evidenceof lithium electrode degradation on cell disassembly, and no evidence ofgas buildup due to reaction of the lithium with moisture(Li+H₂O═LiOH+½H₂).

Example 3 Long Term Testing of a Protected Lithium Anode Having PolymerAdhesive Seals in Seawater Catholyte

A protected anode was assembled as described in Example 2. Thenon-aqueous anolyte consisted 750 μl of 1.0 M LiClO₄ in propylenecarbonate; the lithium electrode was a circular disk of 2 cm² and 2475μm in thickness; the glass-ceramic membrane was 150 μm thick. Theprotected anode was then immersed in 4 liters of artificial seawater(Ricca Chemical Company) and discharged at a current density of 0.1mA/cm² for seven months. The achieved Li capacity was 506.5 mAh/cm². Thedischarge curve is plotted in FIG. 4. There is no sign of deteriorationof performance due to seawater or non-aqueous solvent permeation throughthe adhesive seal.

Example 4 Long Term Testing of a Protected Lithium Anode Having PolymerAdhesive Seals in Aqueous Catholyte

A protected anode was assembled as described in Example 2. Thenon-aqueous anolyte contained 750 μl of 1.0 M LiPF₆ in propylenecarbonate; the lithium electrode was a circular disk of 2 cm² and 3350μm in thickness; the glass-ceramic membrane was 50 μm thick. Theprotected anode was then immersed in 100 ml of 4M NH₄Cl in distilledwater and discharged at a current density of 0.5 mA/cm² for close to1400 hours. The discharge curve is plotted in FIG. 5. There was no signof deterioration of performance due to water or non-aqueous solventpermeation through the adhesive seal, and 100% of the lithium foilplaced in the anode compartment was discharged during the testdemonstrating a completely hermetic seal stable to aqueous andnon-aqueous solvents and electrolytes.

CONCLUSION

Although the foregoing invention has been described in some detail forpurposes of clarity of understanding, it will be apparent that certainchanges and modifications may be practiced within the scope of theappended claims. It should be noted that there are many alternative waysof implementing both the process and compositions of the presentinvention. Accordingly, the present embodiments are to be considered asillustrative and not restrictive, and the invention is not to be limitedto the details given herein.

All references cited herein are incorporated by reference for allpurposes.

What is claimed is:
 1. A protected anode architecture, comprising: anactive metal anode; a protective membrane architecture conductive toions of the active metal in ionic continuity with the anode; an anodecontainer joined to the protective membrane architecture; at least onepolymeric adhesive seal set at a joint between the protective membranearchitecture and the container, thereby forming a substantiallyimpervious anode compartment having an interior region exclusive of acathode and hermetically sealed from an exterior region; wherein theseal is set at the joint on at least one of an interface between theprotective membrane architecture and the container, and an interfaceedge between the protective membrane architecture and the container,such that the active metal anode is isolated in the anode compartment,while allowing for active metal ion transport into and out of the anodecompartment.
 2. The protected anode architecture of claim 1, wherein theactive metal anode is in the solid phase.
 3. The protected anodearchitecture of claim 2, wherein the active metal anode is at least 10microns thick.
 4. The protected anode architecture of claim 2, whereinthe active metal anode is at least 50 microns thick.
 5. The protectedanode architecture of claim 2, wherein the active metal anode is atleast 1 mm thick.
 6. The protected anode architecture of claim 2,wherein the active metal anode is at least 1 cm thick.
 7. The protectedanode architecture of claim 1, wherein the active metal anode comprisesan alkali metal.
 8. The protected anode architecture of claim 7, whereinthe alkali metal is Li.
 9. The protected anode architecture of claim 7,wherein the alkali metal is Na.
 10. The protected anode architecture ofclaim 1, wherein the active metal anode comprises active metal-ions. 11.The protected anode architecture of claim 1, wherein the active metalanode comprises active metal alloying metal.
 12. The protected anodearchitecture of claim 11, wherein the active metal alloying metal isselected from the group consisting of Ca, Mg, Sn, Ag, Bi, Al, Cd, Ga, Inand Sb.
 13. The protected anode architecture of claim 1, wherein theactive metal anode comprises intercalating material.
 14. The protectedanode architecture of claim 13, wherein the active metal intercalatingmaterial comprises carbon.
 15. The protected anode architecture of claim1, wherein the protective membrane architecture comprises an ionicallyconductive solid state membrane.
 16. The protected anode architecture ofclaim 15, wherein the solid state membrane has an ionic conductivity ofat least 10⁻⁵ S/cm.
 17. The protected anode architecture of claim 15,wherein the solid state membrane has an ionic conductivity of at least10⁻³ S/cm.
 18. The protected anode architecture of claim 15, wherein thesolid state membrane is monolithic.
 19. The protected anode architectureof claim 15, wherein the solid state membrane comprises a compositecomprising, a first material component in contact with the anode that isionically conductive and chemically compatible with the active metal ofthe anode, and a second material component in contact with the firstmaterial component, the second material being substantially impervious,ionically conductive and chemically compatible with the first materialcomponent and the exterior of the anode compartment.
 20. The protectedanode architecture of claim 19, wherein the composite is a laminate. 21.The protected anode architecture of claim 19, wherein composite isgraded.
 22. The protected anode architecture of claim 19, wherein thefirst component comprises a material selected from the group consistingof active metal nitrides, active metal phosphides, and active metalhalides, and active metal phosphorus oxynitride glass.
 23. The protectedanode architecture of claim 19, wherein the first component comprises amaterial selected from the group consisting of Li₃N, Li₃P and LiI, LiBr,LiCl, LiF and LiPON, Li-sulfide, Li-phosphorous sulfide, Li₂S—P₂S₅,Li₂S—P₂S₅—LiI.
 24. The protected anode architecture of claim 19, whereinthe first component comprises a metal nitride first layer materialprecursor.
 25. The protected anode architecture of claim 19, wherein thefirst component comprises the reaction product of Cu₃N and Li.
 26. Theprotected anode architecture of claim 19, wherein the second componentcomprises a material selected from the group consisting of glassy oramorphous metal ion conductors, ceramic active metal ion conductors, andglass-ceramic active metal ion conductors.
 27. The component of claim 19wherein the second component comprises a material selected from thegroup consisting of phosphorous based glass, oxide based glass, sulfurbased glass, oxide sulfur based glass, selenide based glass, galliumbased glass, germanium based glass, glass ceramic active metal ionconductors, sodium beta-alumina and lithium beta-alumina, Li superionicconductor (LISICON), Na superionic conductor (NASICON), LiPON,Li₃PO₄.Li₂S.SiS₂, Li₂S.GeS₂.Ga₂S₃, Li₂O.11Al₂O₃, Na₂O.11Al₂O₃,Nasiglass, Li_(0.3)La_(0.5)TiO₃, Na₅MSi₄O₁₂ (M: rare earth such as Nd,Gd, Dy), (Na, Li)_(1+x)Ti_(2−x)Al_(x)(PO₄)₃ (0.0≦x≦0.9) andcrystallographically related structures, Li_(1+x)Hf_(2−x)Al_(x)(PO₄)₃(0.0≦x≦0.9), Na₃Zr₂Si₂PO₁₂, Li₃Zr₂Si₂PO₁₂, Na₅ZrP₃O₁₂, Na₅TiP₃O₁₂,Na₃Fe₂P₃O₁₂, Na₄NbP₃O₁₂, Li₅ZrP₃O₁₂, Li₅TiP₃O₁₂, Li₃Fe₂P₃O₁₂ andLi₄NbP₃O₁₂.
 28. The protected anode architecture of claim 26, whereinthe second component is an ion conductive glass-ceramic having thefollowing composition: Composition Mol % P₂O₅ 26-55%  SiO₂ 0-15% GeO₂ +TiO₂ 25-50%  in which GeO₂ 0-50% TiO₂ 0-50% ZrO₂ 0-10% M₂O₃ 0-10% Al₂O₃0-15% Ga₂O₃ 0-15% Li₂O 3-25%

and containing a predominant crystalline phase composed ofLi_(1+x)(M,Al,Ga)_(x)(Ge_(1−y)Ti_(y))_(2−x)(PO₄)₃ where X≦0.8 and0≦Y≦1.0, and where M is an element selected from the group consisting ofNd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/orLi_(1+x+y)Q_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ where 0<X≦0.4 and 0<Y≦0.6, andwhere Q is Al or Ga.
 29. The protected anode architecture of claim 1,wherein the protective membrane architecture comprises, an active metalion conducting separator layer chemically compatible with the activemetal of the anode and in contact with the anode, the separator layercomprising a non-aqueous anolyte, and a substantially impervious,ionically conductive layer in contact with the separator layer, andchemically compatible with the separator layer and with the exterior ofthe anode compartment.
 30. The protected anode architecture of claim 29,wherein the separator layer comprises a semi-permeable membraneimpregnated with a non-aqueous anolyte.
 31. The protected anodearchitecture of claim 30, wherein the semi-permeable membrane is amicro-porous polymer.
 32. The protected anode architecture of claim 31,wherein the anolyte is in the liquid phase.
 33. The protected anodearchitecture of claim 32, wherein the anolyte comprises a solventselected from the group consisting of organic carbonates, ethers,esters, formates, lactones, sulfones, sulfolane and combinationsthereof.
 34. The protected anode architecture of claim 33, wherein theanolyte comprises a solvent selected from the group consisting of EC,PC, DEC, DMC, EMC, THF, 1,3-dioxolane, 2MeTHF, 1,2-DME or higher glymes,sufolane, methyl formate, methyl acetate, and combinations thereof and asupporting salt selected from the group consisting of LiPF₆, LiBF₄,LiAsF₆, LiClO₄, LiSO₃CF₃, LiN(CF₃SO₂)₂ and LiN(SO₂C₂F₅)₂, NaClO₄, NaPF₆,NaAsF₆ NaBF₄, NaSO₃CF₃, NaN(CF₃SO₂)₂ and NaN(SO₂C₂F₅)₂.
 35. Theprotected anode architecture of claim 34, wherein the anolyte is in thegel phase.
 36. The protected anode architecture of claim 35, wherein theanolyte comprises a gelling agent selected from the group consisting ofPVdF, PVdF-HFP copolymer, PAN, and PEO and mixtures thereof; aplasticizer selected from the group consisting of EC, PC, DEC, DMC, EMC,THF, 2MeTHF, 1,2-DME, 1,3-dioxolane and mixtures thereof; and a Li saltselected from the group consisting of LiPF₆, LiBF₄, LiAsF₆, LiClO₄,LiSO₃CF₃, LiN(CF₃SO₂)₂ and LiN(SO₂C₂F₅)₂, NaClO₄, NaPF₆, NaAsF₆ NaBF₄,NaSO₃CF₃, NaN(CF₃SO₂)₂ and NaN(SO₂C₂F₅)₂.
 37. The protected anodearchitecture of claim 29, wherein the substantially impervious ionicallyconductive layer comprises a material selected from the group consistingof glassy or amorphous active metal ion conductors, ceramic active metalion conductors, and glass-ceramic active metal ion conductors.
 38. Thecomponent of claim 29 wherein the second component comprises a materialselected from the group consisting of phosphorous based glass, oxidebased glass, sulfur based glass, oxide sulfur based glass, selenidebased glass, gallium based glass, germanium based glass, glass ceramicactive metal ion conductors, sodium beta-alumina and lithiumbeta-alumina, Li superionic conductor (LISICON), Na superionic conductor(NASICON), LiPON, Li₃PO₄.Li₂S.SiS₂, Li₂S.GeS₂.Ga₂S₃, Li₂O.11Al₂O₃,Na₂O.11Al₂O₃, Nasiglass, Li_(0.3)La_(0.5)TiO₃, Na₅MSi₄O₁₂ (M: rare earthsuch as Nd, Gd, Dy), (Na, Li)_(1+x)Ti_(2−x)Al_(x)(PO₄)₃ (0.0≦x≦0.9) andcrystallographically related structures, Li_(1+x)Hf_(2−x)Al_(x)(PO₄)₃(0.0≦x≦0.9) Na₃Zr₂Si₂PO₁₂, Li₃Zr₂Si₂PO₁₂, Na₅ZrP₃O₁₂, Na₅TiP₃O₁₂,Na₃Fe₂P₃O₁₂, Na₄NbP₃O₁₂, Li₅ZrP₃O₁₂, Li₅TiP₃O₁₂, Li₃Fe₂P₃O₁₂ andLi₄NbP₃O₁₂.
 39. The protected anode architecture of claim 29, whereinsubstantially impervious ionically conductive layer is an ion conductiveglass-ceramic having the following composition: Composition mol % P₂O₅26-55%  SiO₂ 0-15% GeO₂ + TiO₂ 25-50%  in which GeO₂ 0-50% TiO₂ 0-50%ZrO₂ 0-10% M₂O₃ 0-10% Al₂O₃ 0-15% Ga₂O₃ 0-15% Li₂O 3-25%

and containing a predominant crystalline phase composed ofLi_(1+x)(M,Al,Ga)_(x)(Ge_(1−y)Ti_(y))_(2−x)(PO₄)₃ where X≦0.8 and0≦Y≦1.0, and where M is an element selected from the group consisting ofNd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb and/orLi_(1+x+y)Q_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ where 0<x≦0.4 and 0<Y≦0.6, andwhere Q is Al or Ga.
 40. The protected anode architecture of claim 1,wherein the polymeric adhesive seal is an epoxy.
 41. The protected anodearchitecture of claim 40, wherein the polymeric adhesive epoxy sealcomprises polyamide.
 42. The protected anode architecture of claim 40wherein the polymeric adhesive seal is substantially impervious toaqueous catholyte and anolyte comprising organic solvents.
 43. Theprotected anode architecture of claim 1, wherein the polymeric adhesiveseal comprises a thermoplastic.
 44. The protected anode architecture ofclaim 43, wherein the polymeric adhesive seal comprises a material fromthe group consisting polyethylene, polypropylene, ethylene vinylacetate, ethylene acrylic acid, tetrafluoroethylene, hexafluoropropyleneand acid modified ethylene acids.
 45. The protected anode architectureof claim 1, wherein the polymeric adhesive seal comprisespolyisobutylene having a molecular weight in the range of 60,000 to5,000,000.
 46. The protected anode architecture of claim 1, wherein theprotective membrane architecture and the container are sealed by atleast two polymer adhesive seals having different composition orstructure.
 47. The protected anode architecture of claim 46, wherein apolymer adhesive seal is set at the interface edge on the interior wallof the anode compartment and a second polymer adhesive seal having adifferent composition or structure is set at the interface edge on theexterior wall of the compartment.
 48. The protected anode architectureof claim 47, wherein the polymer adhesive seal on the interior wall ofthe anode compartment is substantially impervious to components that itcontacts from the interior environment of the anode compartment and thedifferent polymer adhesive seal on the exterior wall of the anodecompartment is substantially impervious to components that it contactsfrom the exterior environment.
 49. The protected anode architecture ofclaim 1, further comprising a bonding agent.
 50. The architecture ofclaim 1, wherein the environment exterior to the anode compartmentcomprises a cathode system comprising catholyte and a cathode structure.51. The architecture of claim 50, wherein the catholyte comprises water.52. The architecture of claim 51, wherein the catholyte comprises wateras an electrochemically active component.
 53. The architecture of claim51, wherein the catholyte further comprises a water soluble oxidantselected from the group consisting of gaseous, liquid and solid oxidantsand combinations thereof.
 54. The architecture of claim 53, wherein thewater soluble gaseous oxidants are selected from the group consisting ofSO₂, NO₂, O₂, and the water soluble oxidants are selected from the groupconsisting of NaNO₂, KNO₂, Na₂SO₃ and K₂SO₃.
 55. The architecture ofclaim 53, wherein the water soluble oxidant is a peroxide.
 56. Thearchitecture of claim 55, wherein the water soluble oxidant is hydrogenperoxide.
 57. The architecture of claim 51, wherein the aqueouscatholyte is selected from the group consisting of strong acidsolutions, weak acid solutions, basic solutions, neutral solutions,amphoteric solutions, peroxide solutions and combinations thereof. 58.The architecture of claim 57, wherein the aqueous catholyte comprisesmembers selected from the group consisting of aqueous solutions of HCl,H₂SO₄, H₃PO₄, acetic acid/Li acetate, LiOH; seawater, LiCl, LiBr, LiI,NH4Cl, NH4Br and hydrogen peroxide, and combinations thereof.
 59. Thearchitecture of claim 58, wherein the aqueous catholyte is sea water.60. The architecture of claim 58, wherein the aqueous catholytecomprises sea water and hydrogen peroxide.
 61. The architecture of claim50, wherein the cathode system comprises a cathode structure comprisingan intercalation compound selected from the group consisting of V₂O₅,V₆O₁₃, Li_(x)CoO₂, Li_(x)NiO₂, Li_(x)Mn₂O₄, LiFePO₄, Li₃V₂(PO₄)₃, andLi₃V₂P₃O₁₁F.
 62. The architecture of claim 61, wherein the catholytecomprises a non-aqueous solvent.
 63. A method of making a protectedanode architecture, comprising: providing an active metal anode in ioniccontinuity with an ionically conductive protective membrane architectureconductive to ions of the active metal; and joining an anode containerto the protective membrane architecture to form an anode compartmenthaving an interior region exclusive of a cathode and hermetically sealedfrom an exterior region; wherein the joining comprises sealing the anodecompartment at a joint between the membrane architecture and thecontainer by one or more polymer adhesive seals; wherein the one or morepolymer adhesive seals is set at the joint on at least one of aninterface between the protective membrane architecture and thecontainer, and an interface edge between the protective membranearchitecture and the container, such that the active metal anode isisolated in the anode compartment, while allowing for active metal iontransport into and out of the anode compartment.
 64. The method of claim63, wherein the polymer adhesive seals are set on at least one of aninterface between the protective membrane architecture and thecontainer, and an interface edge between the protective membranearchitecture and the container located on at least one of the interiorand exterior surface of the anode compartment.
 65. The method of claim64, whereby a single type of polymer adhesive is used to make the seal.66. The method of claim 64, whereby more than one type of polymeradhesive is used to make the seal.
 67. The method of claim 64, wherebythe polymer adhesive seal is cured by a chemical reaction with ahardener.
 68. The method of claim 64, whereby the seal is set at roomtemperature.
 69. The method of claim 68, whereby the polymer adhesive isdissolved in a carrier solvent prior to being set at the joint.
 70. Themethod of claim 69, whereby the polymer adhesive is applied to thebonding surfaces of the joint by brushing.
 71. The method of claim 64,whereby the polymer adhesive is a thermoplastic and applied to thebonding surfaces of the joint by a hot melt applicator.
 72. The methodof claim 64, whereby a bonding agent is used to join the membrane to thecontainer and one type of polymer adhesive is used to make the seal atthe interface edge on the exterior surface of the anode compartment anda different type of polymer adhesive is used to make the interface edgeseal on the interior surface.
 73. The method of claim 64, whereby afirst polymer adhesive is applied at the joint to form a first seal anda second seal is applied over the first seal.
 74. The method of claim63, further comprising combining the protected anode architecture with acathode to form an electrochemical cell.
 75. The method of claim 74,wherein the cell is a battery cell.
 76. The method of claim 75, whereinthe cell is a Li-metal/air battery call.
 77. The method of claim 75,wherein the cell is a Li-metal/seawater battery call.
 78. The method ofclaim 75, wherein the cell is a Li-carbon/transition metal intercalationLi-ion type battery cell.